New dyestuffs



Patented Oct. 9, 1962 ride or phosphorus oxychloride, and especiallythionyl 3,057,876 chloride. NEW DYESTWFS The treatment with theacid-chlorinating agent is ad- 3 555 533g ,Ziigfiigggig 55 vantageouslycarried out in an inert organic solvent, such Na a g Fiiefi 2 2 i N 70373 5 as dimethyl-formamide, a chlorobenzene, for example,

Claims priority, application Switzerland Nov. 26, 1959 monochloro' ordichlom'benzene toluene Xylene or 9v {3325mm (QR 5 trobenzene. When thelast-mentioned solvent is used, the reaction can be accelerated by theaddition of a small This invention provides dyestuffs of the generalforamount of dimethyl-formamide. mula For making the carboxylic acidhalides it is generally 1) (Rah) (B3) 0 ail 4)q 0 R m R z. 1) H N N l 1)(B2) (u I (Ra) GCONHB-NECO (i it in which R R R and R each represent ahydrogen of advantage first to dry the carboxylic acid, which has atomor a substituent not imparting solubility in water been made in anaqueous medium, or to free it from water and any two of whichsubstituents bound in ortho-position azeotropically by boiling it in anorganic solvent. This relatively to one another may form a ring togetherwith azeotropic drying may, if desired, be carried out immedithe vicinalcarbon atoms of the skeleton structure, m, n, ately before the acid istreated with the acid-chlorinating p, and q each represent the wholenumber 1 or 2, and B agent. represents a diphenyl radical free fromgroups imparting As the diamino-diphenyls there are advantageously usedsolubility in water. those of the formula The invention also provides aprocess for the manufacture of the dyestuifs of the general Formula 1,wherein two molecular proportions of a halide of a2:3-phthaloylpyrrocoline-l carboxylic acid of the formula u-l n-l v-lv-l in which X represents a halogen atom or an alkoxy or 5 7 nitrogroup, Y represents a lower alkyl group, and u (R) 6, g I 4)q and v eachrepresent the whole number 1, 2 or 3, and u 1 m 3 N is advantageously atleast as large as v. At least one substituent in each benzene nucleus ispreferably in ortho- 2)u I position to the amino group. Of specialinterest are di- T phenyls of the formula O H2N NHz (the nomenclature inthe pyrrocoline ring is according to I Pattersons Ring Index), in whichformula R R R X1 X1 4 and "b": P and 4 have the meallmgs i P' in which Xrepresents a hydrogen atom or a halogen is condensed with one molecularproportion o a aminoatom or an alkoxy or Him) group.

diphenyl free from groups imparting solubility in water.

In the phthaloyl-pyrrocoline carboxylic acids of the Formula 2 R and Reach preferably represent a hydro- 4:4 p y As examples there may bementioned gen atom or a simple substituent, such as a halogen atom414"diamin-3i3"dichlolodiphenyl,

or a lower alkyl group, and R and R each preferably l y P YL represent ahydrogen atom or a halogen atom, for exam- P Y l hl i or brgmine 4:4'-dam no-3:3'-d methoxy-6:6 drchlorophenyl,

The 2:3-phthaloyl-pyrrocoline carboxylic acids of the Y P Y and Formula2 can be obtained, for example, by the process3'15i5"tetrachlorodlphfinyldescribed in United States Patent No.2,877,230 granted The Condensation of the P Y -PY CaTbOX- M h 10 1959 tR b t S L et 1 b condensing ylic acid halides with the diamines isadvantageously cara 2:3-dichloro-naphthoquinone with an acetoacetic acidTied F In an anhydrous medlllmt ea e he conalkyl ester and pyridine or asubstitution product thereof, densatlon gfifflefally takeisplacesurpflsillgly Y at f f l i li d h d l i h resulting 6 peratures withinthe boiling ranges of the ordinary inert alkyl ester to form thecanboxylic acid. As suitable naphorganw solvents, such as toluene,monochloro-benzene, thoquinones there may be mentioned more especially,on dichlofo-benzefle, tfl'chlorwbenleflfi, Milo-benzene an account ofthe a ith whi h it can b bt i d, 23. the like. In order to acceleratethe reaction there may dichloro-naphthoquinone. There may also bementioned be used an acid-binding n SllCh a anhydrous Sodium 2:3:5- or2:3:6-trichloro-naphthoquinone, 2:3-dibromoacetate, pyridine oranhydrous ammonia The dyestuffs naphthoquinone and 213:6:7-tetrabromonaphthoquinone. are generally obtained in very good yieldsand in a pure There are advantageously used chlorides of 213- state. Itmay be of advantage in order to obtain espephthaloyl-pyrrocolinecarboxylic acids. These chlorides ,Cially pure dyestuffs to precipitatethe acid chloride obcan be obtained in known manner by treating theapprotained from the carboxylic acid and, if desired, to repriatecarboxylic acid with an acid-chlorinating agent, for crystallize theacid chloride. In most cases, especially example, phosphorustrichloride, phosphorus pentachlowhen thionyl chloride is used asac1d-chlor1nat1ng agent,

the precipitation of the acid chloride can be dispensed with withoutharm, and in some cases even with better results, and the condensationcarried out immediately following the preparation of the carboxylic acidchloride.

The dyestufis of the invention are useful for dyeing a very wide varietyof materials, for example, they are useful as vat dyestuffs for dyeingcellulose fibers or animal fibers, such as wool or silk, or syntheticfibers, such as polyamide or polyester fibers. The dyestufis of theinvention may be sulfonated and used in that state for dyeing theaforesaid fibers, especially animal fibers. They are also suitable foruse as pigments in all applications for which pigments are used, forexample, in so-called pigment printing that is to say, the method ofprinting in which a pigment is fixed on a substratem, especially on atextile fiber, or on other flat structures, such as paper, for example,wallpaper, or fabrics of glass fibers, by means of a suitable adhesive,such as casein, a hardenable synthetic product, especially a ureaormelamine-formaldehyde condensation product, a solution or emulsion ofpolyvinyl chloride or polyvinyl acetate or other emulsion, for example,an oil-in-water or water-inoil emulsion. The pigments of the inventioncan also be used for other purposes, for example, in a finely dispersedform for dyeing in the spinning mass rayon of viscose or of a celluloseether or ester or of a polyamide or polyurethane. They are also veryuseful for the manufacture of colored lacquers or lacquer formers,solutions or products of acetyl-cellulose, nitrocellulose, naturalresins or synthetic resins, such as polymerization resins, for example,polyvinyl chloride or polystyrene, or condensation resins, for example,aminoplasts, phenoplasts, polyethylene, polystyrene, gums, casein,silicones or silicone resins. They are also of advantage in themanufacture of colored pencils, cosmetic preparations and laminatedsheets.

The pigments of this invention, owing to other chemical inertness andgood resistance to temperature, can be dispersed in the normal manner incompositions or products of the kind mentioned above, and this isadvantageously carried out before the compositions of products havereached their final form. The pigments can be converted into a finelydispersed form by the known conditioning methods. The method requiredfor shaping such as spinning, compressing, hardening, casting, stickingor the like, can be carried out in the presence of the pigments.

The pigments of this invention are distinguished by their excellentproperties of fastness to light and migration.

The following examples illustrate the invention, the parts andpercentages being by weight:

Example 1 30.9 parts of 2:3-phthaloyl-pyrrocoline-l-carboxylic acidchloride (obtained in the manner described in US. Patent No. 2,877,230granted March 10, 1959 to Robert S. Long et al. by heating2:3-dichloroor dibromo-naphthoquinone, acetoacetic acid ester andpyridine, hydrolysing the resulting2:3-phthalyl-pyrrocoline-l-carboxylic acid ethyl ester to form thecarboxylic acid, and reacting the latter with thionyl chloride) aresuspended in 750 parts of anhydrous ortho-dichlorobenzene at 115 C.,there is obtained after about 20 minutes a clear solution. Into thesolution is poured in the course of about five minutes a solution,having a temperature of 100 C., of 12.7 parts of4:4-diamino-3:3'-dichloro diphenyl in 100 parts of anhydrousortho-dichloro benzene and 25 parts of anhydrous pyridine. The whole isheated to 140 to 145 C., and that temperature is maintained for abouthours. The Whole is then cooled to 100 C., it is filtered, and thepigment so obtained is washed with orthodichlorobenzene at 100 C. untilthe washings are practically colorless. The pigment is then washed witha small proportion of cold methanol and then with hot water. The pigmentso obtained is dried in vacuo at to C. The pigment when incorporated insheets of polyvinyl chloride yields a yellowish-red tint of goodfastness to migration and light.

The pigment obtained with a 4:4'-diamino-3:3'-dimethoxy diphenyl yieldspolyvinyl chloride sheets having a reddish-blue tint, the pigmentobtained with 4:4'-diamino-Z-nitrodiphenyl yields a neutral red tint andthe pigment prepared with 4:4-diamino-3:3'-dinitro diphenyl yields anorange tint.

Example 2 29.1 parts of 2:3-phthaloyl-pyrrocoline-1-carboxylic acid areheated in 75 0 parts of anhydrous ortho-dichlorobenzene and 40.8 partsof thionyl chloride in the course of about 40 minutes to C. and themixture is maintained at 130 to C. for two hours. Into the resultingsolution of the acid chloride is poured in the course of about fiveminutes a solution, having a temperature of 120 C., of 12.65 parts of3:3'-dichloro-4:4'-diamino diphenyl in 150 parts of anhydrousortho-dichloro benzene and 2:5 parts of anhydrous pyridine. The whole isheated to C. and that temperature is maintained for about 10 hours. Thewhole is then allowed to cool to 100 C., the precipitated pigment isfiltered oil, and the latter is Washed with ortho-dichlorobenzene at 100C. until the washings are practically colorless. The pigment is thenwashed with a small amount of methanol and with hot water. The pigmentis dried in vacuo at 90 to 100 C. There is obtained a pigment having thesame properties as the pigment obtained as described in Example 1.

Example 3 34.4 parts of 4'- or 5-chloro-2:3-phthaloyl-pyrrocolinecarboxylic acid chloride, dissolved in 750 parts of anhydrousortho-dichlorobenzene at 115 C., are mixed with a solution of 12.2 partsof 3:3'-dimethoxy-4:4-diamino-diphenyl, dissolved in 150 parts ofanhydrous ortho-dichloro-benezene, and 2.5 parts of anhydrous pyridineat 120 C. The pigment so obtained colors polyvinyl chloride sheets greytints of good fastness to migration.

By using, instead of 3:3'-dimethoxy-4:4-diamino diphenyl, an equivalentquantity of 4:4'-diamino diphenyl there is obtained a pigment which Whenrolled into polyvinyl chloride sheets produces a violet tint. By usingin a similar manner the pigment obtained with 3:3-dichloro-4:4-diamino-diphenyl, there is obtained a reddish-violet tint, thepigment obtained with 3:3-dinitro-4:4'-diamino diphenyl yields a scarlettint and the pigment obtained with 3 :3'-dimethoxy-66'-dichloro-4:4-diamino diphenyl yields a violet tint.

Example 4 65 parts of polyvinyl chloride, 35 parts of dioctylphthalateand 0.2 part of the pigment, obtained as described in the firstparagraph of Example 1, are stirred together and the mixture is rolledto and fro in a two-roller calender for 7 minutes at C. There isobtained a yellowishred sheet of good fastness to light and migration.By using, in addition to the aforesaid quantity of pigment, five partsof titanium dioxide there is obtained a yellowish-red pastel tint.

Example 5 0.25 part of the dyestuff as described in the first paragraphof Example 1 is ground for 24 hours in a rod mill with 40 parts of analkyd-melamine bakeable lacquer, which contains 50% of solid matter, and4.75 parts of titanium dioxide. The lacquer so obtained is brushed inthe form of a thin coating on a sheet of aluminum, and the coating isbaked for one hour at 120 C. There is obtained a yellowing-red coatingof good fastness to light.

Example 6 The following separate layers are prepared for making alaminate:

(a) Strong paper of unbleached sulfate cellulose (so nate is removedfrom the press. The laminate has one called kraft paper) is impregnatedwith an aqueous soluside a scarlet-red coloration of good fastness tolight. 332d of a phenol-formaldehyde resin, and then pressed and Example7 (b) Paper of pure chemically bleached cellulose con- 1 P Of thedyesfilfi Obtained as described in EXamPIe taining zinc sulfide ortitanium dioxide as filler is impreg- ,5 3 with the use of 4:4'-diaminodiphenyl as diamine is nated with an aqueous solution ofdimethylol-melamine Vattfid in 100 Parts Of Water With tW Parts OfSodium yof 50% strength, then pressed and dried at 100 C. drosulfate at45 C. with the addition of 4 parts by volume (0) 400 parts of decorationpaper of bleached cellulose Of a Sodium ydr Solution ofStrengthcontaining zinc sulfide or titanium dioxide as filler are dis- TStock Va 80 a n d s add d 0 a So ution Of 4 integrated in a Hollanderwith 10,000 parts of Water. To 10 parts by volume of a sodium hydroxideS l t on of 30% the paper pulp so obtained there are added 30 parts of aStrength and 2 Parts of Sodium hydlosulfile in 2,000 Part5 pigmentobtained as described in Example 1. The pigof Water. In the dyebath soobtained are dyed 100 parts ment is fixed by the addition of 16 parts ofaluminum sulof cotton for one hour at 40 to 50 C. With the additionfate. The colored decoration paper is impregnated in an of Parts OfSodium Chloride- The 601513011 is then aqueous solution ofdimethylolqmelamine of 50% strength squeezed, OXidiSed in the rinsed,acidified, again rinsed and then pressed and dried at 100 C, and soapedat the boil. There is obtained a violet dyeing (d) Depending on thequality of the laminate to be having y good P p i of faStIleSS-produced, the decoration paper may be protected with What is claimed is:tissue-paper of bleached special cellulose, the tissue-paper 1. Adyestufr of the formula R1 I l R; R2 NHO o-hn halogen halogen C)weighing grams per square meter. The tissue-paper is in which R R R andR each represents a member sealso impregnated with an aqueous solutionof dimethylollected from the group consisting of hydrogen, halogen andmelamine of strength, then pressed and dried at lower alkyl. C. 2. Adyestutf of the formula R: R: l?

R J R1 O0NH NH-C o- (l lower lower C]! alkoxy alkoxy in which R R R andR each represents a member se- Sheets of the materials prepared asdescribed above lected from the group consisting of hydrogen, halogenand being the same size, for example, measuring 2.75 meters lower alkyl.

3. A dyestufi of the formula by 1.25 meters, are placed one upon theother as follows: 60 in which R R R and R each represents a member se-First 3 to 5 layers of paper (a) then one layer of paper 1 lected fromthe group consisting of hydrogen, halogen (b) one layer of paper (0)and, if desired, a layer of and lower alkyl. paper (d). The assembly ispressed between highly glossy 4. A dyestutf of the formula chromiumplated plates for 12 minutes at to C. in which R R R and R eachrepresents a member seunder a pressure of 100 kilograms per square cm.The lected from the group consisting of hydrogen, halogen assembly isthen cooled to 30 C. and the resulting lami- 75 and lower alkyl.

5. The dyestufi of the formula 0 I 0 II I N I 1 Y t 0 0 6. The dyestufiof the formula 6 N i I w I ll 0 O 7. The dyestufi of the formula t N l lN R 8. The dyestufl of the formula l t N N02 X 0 I I0 X H N N 0 0 l l lL X O X wherein one X of each pair of the symbols X attached to the samecarboxylic acid residue is chlorine and the other is hydrogen.

References Cited in the file of this patent UNITED STATES PATENTS2,772,274 Schmidt-Nickels et a1. Nov. 27, 1956 2,773,873 Randall et a1Dec. 11, 1956 2,877,230 Long et a1 Mar. 10, 1959 OTHER REFERENCESNoller: Chemistry of Organic Compounds (1957), p.

549 (Saunders).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No, 3,057,870 October 9, 1962 Eduard Moser It is hereby certified that errorappears in the above numbered patent requiring correction and that thesaid Letters Patent should read as corrected below.

Column 3, line 15, for "substratem" read substratum column 4, line 39,for "benezene" read benzene 3 column 7,

.the center part of the formulae of claims 5 and 9., should appear asshown below instead of as in the patent:

Signed and sealed this 17th day of Sept-ember 1963 :SEAL) Attest: ERNESTW. SWIDER DAVID L. LADD Attesting Officer Commissioner of Patents

1. A DYESTUFF OF THE FORMULA